6,467 research outputs found
Femtosecond probing of bimolecular reactions: The collision complex
Progress has been made in probing the femtosecond
dynamics of transition states of chemical reactions.(1) The
"half-collision" case of unimolecular reactions has been
experimentally investigated for a number of systems and
much theoretical work has already been developed.(2) For
bimolecular reactions, the case of full collision, the zero of
time is a problem which makes the femtosecond temporal
resolution of the dynamics a difficult task
Femtosecond real-time probing of reactions. VIII. The bimolecular reaction Br+I2
In this paper, we discuss the experimental technique for real-time measurement of the lifetimes of the collision complex of bimolecular reactions. An application to the atom–molecule Br+I_2 reaction at two collision energies is made. Building on our earlier Communication [J. Chem. Phys. 95, 7763 (1991)], we report on the observed transients and lifetimes for the collision complex, the nature of the transition state, and the dynamics near threshold. Classical trajectory calculations provide a framework for deriving the global nature of the reactive potential energy surface, and for discussing the real-time, scattering, and asymptotic (product-state distribution) aspects of the dynamics. These experimental and theoretical results are compared with the extensive array of kinetic, crossed beam, and theoretical studies found in the literature for halogen radical–halogen molecule exchange reactions
Cartan subalgebras in C*-algebras of Hausdorff etale groupoids
The reduced -algebra of the interior of the isotropy in any Hausdorff
\'etale groupoid embeds as a -subalgebra of the reduced
-algebra of . We prove that the set of pure states of with unique
extension is dense, and deduce that any representation of the reduced
-algebra of that is injective on is faithful. We prove that there
is a conditional expectation from the reduced -algebra of onto if
and only if the interior of the isotropy in is closed. Using this, we prove
that when the interior of the isotropy is abelian and closed, is a Cartan
subalgebra. We prove that for a large class of groupoids with abelian
isotropy---including all Deaconu--Renault groupoids associated to discrete
abelian groups--- is a maximal abelian subalgebra. In the specific case of
-graph groupoids, we deduce that is always maximal abelian, but show by
example that it is not always Cartan.Comment: 14 pages. v2: Theorem 3.1 in v1 incorrect (thanks to A. Kumjain for
pointing out the error); v2 shows there is a conditional expectation onto
iff the interior of the isotropy is closed. v3: Material (including some
theorem statements) rearranged and shortened. Lemma~3.5 of v2 removed. This
version published in Integral Equations and Operator Theor
Simonsenia aveniformis sp nov (Bacillariophyceae), molecular phylogeny and systematics of the genus, and a new type of canal raphe system
The genus Simonsenia is reviewed and S. aveniformis described as new for science by light and electron microscopy. The new species originated from estuarine environments in southern Iberia (Atlantic coast) and was isolated into culture. In LM, Simonsenia resembles Nitzschia, with bridges (fibulae) beneath the raphe, which is marginal. It is only electron microscope (EM) examination that reveals the true structure of the raphe system, which consists of a raphe canal raised on a keel (wing), supported by rib like braces (fenestral bars) and tube-like portulae; between the portulae the keel is perforated by open windows (fenestrae). Based on the presence of portulae and a fenestrated keel, Simonsenia has been proposed to be intermediate between Bacillariaceae and Surirellaceae. However, an rbcL phylogeny revealed that Simonsenia belongs firmly in the Bacillariaceae, with which it shares a similar chloroplast arrangement, rather than in the Surirellaceae. Lack of homology between the surirelloid and simonsenioid keels is reflected in subtle differences in the morphology and ontogeny of the portulae and fenestrae. The diversity of Simonsenia has probably been underestimated, particularly in the marine environment.Polish National Science Centre in Cracow within the Maestro program [N 2012/04/A/ST10/00544]; Sciences and Technologies Foundation-FCT (Portugal) [SFRH/BD/62405/2009]info:eu-repo/semantics/publishedVersio
An adaptive Metropolis-Hastings scheme: sampling and optimization
We propose an adaptive Metropolis-Hastings algorithm in which sampled data
are used to update the proposal distribution. We use the samples found by the
algorithm at a particular step to form the information-theoretically optimal
mean-field approximation to the target distribution, and update the proposal
distribution to be that approximatio. We employ our algorithm to sample the
energy distribution for several spin-glasses and we demonstrate the superiority
of our algorithm to the conventional MH algorithm in sampling and in annealing
optimization.Comment: To appear in Europhysics Letter
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Beagle 2: Mission to Mars — current status
Beagle 2, developed in the UK, was launched on June 2, 2003. It landed on Mars on December 25th, 2003 in Isidis Planitia, a large sedimentary basin. To date, the team is awaiting signals from the Beagle 2 lander. Current status of the mission will be reported
Approaches towards expression profiling the response to treatment
Over the past 8 years there has been a wealth of breast cancer gene expression studies. The majority of these studies have focused upon characterising a tumour at presentation, before treatment, rather than looking at the effects of treatment on the tumour. More recently, a number of groups have moved from predicting prognosis based upon long-term follow-up to alternative approaches of using expression profiling to measure the effect of treatment on breast tumours and potentially predict response to therapy using either post-treatment samples or both pre-treatment and post-treatment samples. Whilst this provides great potential to further our understanding of the mode of action of treatments and to more accurately select which patients will benefit from a particular treatment, serious issues of experimental design must be considered
Pipeline network features and leak detection by cross-correlation analysis of reflected waves
This paper describes progress on a new technique to detect pipeline features and leaks using signal processing of a pressure wave measurement. Previous work (by the present authors) has shown that the analysis of pressure wave reflections in fluid pipe networks can be used to identify specific pipeline features such as open ends, closed ends, valves, junctions, and certain types of bends. It was demonstrated that by using an extension of cross-correlation analysis, the identification of features can be achieved using fewer sensors than are traditionally employed. The key to the effectiveness of the technique lies in the artificial generation of pressure waves using a solenoid valve, rather than relying upon natural sources of fluid excitation. This paper uses an enhanced signal processing technique to improve the detection of leaks. It is shown experimentally that features and leaks can be detected around a sharp bend and up to seven reflections from features/ leaks can be detected, by which time the wave has traveled over 95 m. The testing determined the position of a leak to within an accuracy of 5%, even when the location of the reflection from a leak is itself dispersed over a certain distance and, therefore, does not cause an exact reflection of the wave
New development: Directly elected mayors in Italy: creating a strong leader doesn’t mean creating strong leadership
More than 20 years after their introduction, directly elected mayors are key players in Italian urban governance. This article explains the main effects of this reform on local government systems and provides lessons for other countries considering directly elected mayors
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